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Results for “optimized energy density functionals”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Gauge theory for the cuprates near optimal doping

We describe the phase diagram of a 2+1-dimensional SU(2) gauge theory of fluctuating incommensurate spin density waves for the hole-doped cuprates. Our primary assumption is that all low-energy fermionic excitations are gauge neutral and electron-like, while the spin density wave order is fractionalized into Higgs fields transforming as adjoints of the gauge SU(2). The confining phase of the gauge theory is a conventional Fermi liquid with a large Fermi surface (and its associated d-wave superconductor). There is a quantum phase transition to a Higgs phase describing the “pseudogap” at lower doping. Depending on the quartic terms in the Higgs potential, the Higgs phase exhibits one or more of charge density wave, Ising-nematic, time-reversal odd scalar spin chirality, and Z 2 topological orders. It is notable that the emergent broken symmetries in our theory of fluctuating spin density waves coincide with those observed in diverse experiments. For the electron-doped cuprates, the spin density wave fluctuations are at wave vector (π,π), and then the corresponding SU(2) gauge theory only has a crossover between the confining and Higgs regimes, with an exponentially large confinement scale deep in the Higgs regime. Here, on the Higgs side, for both the electron- and hole-doped cases, and at scales shorter than the confinement scale (which can be infinite when Z 2 topological order is present), the electron spectral function has a “fractionalized Fermi liquid” form with small Fermi surfaces. We also describe the deconfined quantum criticality of the Higgs transition in the limit of a large number of Higgs flavors, and perturbatively discuss its coupling to fermionic excitations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Molecular Level Understanding of Polyethylene Terephthalate (PET) Depolymerization in Base/Alcohol Hybrid Systems

Polyethylene terephthalate (PET) depolymerization in base/alcohol hybrid systems represents a promising low-energy approach for chemically recycling PET waste into valuable monomers. This study investigates the mechanistic pathways of PET depolymerization in NaOH/alcohol solutions, emphasizing the competing roles of hydroxide and alkoxide species. Utilizing a combination of experimental techniques, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations, we explore how factors such as base concentration, alcohol chain length, and pKa values of alcohols influence PET depolymerization efficiency and pathways. Our findings indicate that alkoxide ions (RO⁻) exhibit notably higher reactivity than hydroxide ions (HO⁻), favoring an alcoholysis pathway in the base/alcohol hybrid system. Experimental results across a series of C1 to C5 alcohols show that longer-chain alcohols, particularly 1-butanol, achieve higher PET conversion, although this does not align solely with simple nucleophilicity trends of alkoxides. While DFT calculations reveal comparable activation energies for various alkoxides in PET depolymerization, MD simulations underscore the significant role of alcohol chain length, with longer-chain alcohols forming more stable or frequent interactions with PET. Additionally, the alkoxide concentration, influenced by the alcohol’s pK a , directly impacts PET conversion. These suggest that PET depolymerization is governed by a balance between alkoxide concentration and alkoxide-PET interactions, rather than activation energies or nucleophilicity alone. From a practical perspective, incorporating long-chain alcohols as cosolvents may enhance process efficiency but increases raw material costs by approximately 30%. However, long-chain alcohols present a safer and more sustainable alternative to hazardous cosolvents such as dichloromethane. This work offers a molecular-level understanding of PET depolymerization in base/alcohol systems and provides insights into optimizing these systems for more efficient and sustainable PET recycling processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Impact of baryonic processes on weak-lensing cosmology: Power spectrum, nonlocal statistics, and parameter bias

We study the impact of baryonic physics on cosmological parameter estimation with weak-lensing surveys. We run a set of cosmological hydrodynamics simulations with different galaxy formation models. We then perform ray-tracing simulations through the total matter density field to generate 100 independent convergence maps with a field of view of 25 deg{sup 2}, and we use them to examine the ability of the following three lensing statistics as cosmological probes: power spectrum (PS), peak counts, and Minkowski functionals (MFs). For the upcoming wide-field observations, such as the Subaru Hyper Suprime-Cam (HSC) survey with a sky coverage of 1400 deg{sup 2}, these three statistics provide tight constraints on the matter density, density fluctuation amplitude, and dark energy equation of state, but parameter bias is induced by baryonic processes such as gas cooling and stellar feedback. When we use PS, peak counts, and MFs, the magnitude of relative bias in the dark energy equation of state parameter w is at a level of, respectively, δw∼0.017, 0.061, and 0.0011. For the HSC survey, these values are smaller than the statistical errors estimated from Fisher analysis. The bias could be significant when the statistical errors become small in future observations with a much larger survey area. We find that the bias is induced in different directions in the parameter space depending on the statistics employed. While the two-point statistic, i.e., PS, yields robust results against baryonic effects, the overall constraining power is weak compared with peak counts and MFs. On the other hand, using one of peak counts or MFs, or combined analysis with multiple statistics, results in a biased parameter estimate. The bias can be as large as 1σ for the HSC survey and will be more significant for upcoming wider-area surveys. We suggest to use an optimized combination so that the baryonic effects on parameter estimation are mitigated. Such a “calibrated” combination can place stringent and robust constraints on cosmological parameters.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Development of an Anode Stabilization Layer for High Energy Li-S Cells for Electric Vehicles

For lithium-Sulfur (Li-S) batteries to be practical, economic and safe for powering electric vehicles more than 300 miles between charges the energy and cycle life must be improved. Li- S’s theoretical specific energy and energy density are (2,550 Wh/kg, 2,860 Wh/l), compared to (~600 Wh/kg, 1,800 Wh/l) for Li-ion. At less than 25% of theoretical specific energy (~560 Wh/kg at the cell level), Li-S batteries could power a 1500 kg, 5 passenger vehicle, more than 300 miles between charges with a battery pack weighing less than 300 kg. For commercial viability these cells must be safe, low cost and exhibit more than 1,000 full depth of discharge cycles. By implementing unique new physical barrier technologies this work targets (500 Wh/kg, 500 cycles) at the cell level by late 2013. After this program, (600 Wh/kg, 1,000 cycles) cells are targeted in >40 kWh battery packs by 2018 at < $200/kWh. The present state-of-the-art Li-S cells developed at Sion Power, in current commercial format delivers (2.8 Ah, 5.8 Wh, 350 Wh/kg) and are limited to ~50 cycles. These cells deliver only 14% of theoretical specific energy. By retooling and optimizing cell design and packaging to rebalance materials, this chemistry can reach (350 Wh/kg, ~100 cycles) in commercial cells. Much more than 100 cycles, at >350 Wh/kg, is unlikely for the present chemistry-only Li-S cell paradigm. Cycle life is limited almost exclusively by reactions between the Li-metal anode and the solvents necessary to promote cathode function. To release the transformational energy of Li-S the anode must be decoupled from the cathode chemistry. Prospects to achieve this decoupling through chemistry alone are challenging, therefore this program is to accelerate efforts to decouple anode and cathode chemistries by separating the electrodes with ion selective, thin film multi-layer, physical barrier membranes stabilized by externally applied pressure. This report will focus on efforts of Battelle to develop an anode stabilization layer and method to measure the ionic conductivity of this thin vacuum deposited polymeric layer.

Gross, M. E.↗
DOE OSTI2023

Uncovering the mechanism of selective stabilization of high-energy diastereoisomers via inclusion

Abstract Supramolecular systems may be used to stabilize otherwise unstable isomers to find alternative synthetic pathways. It has been reported that cucurbit[8]uril can stabilize trans -I and trans -II Cu $$^{{\textrm{II}}}$$ II cyclam, whereas trans -III is the only non-substituted trans Cu $$^{{\textrm{II}}}$$ II cyclam diastereoisomer found outside of the host molecule experimentally. Quantum chemistry methods can provide valuable insight into the intermolecular interactions involved in these inclusion complexes. All five possible trans diastereoisomers of Cu $$^{{\textrm{II}}}$$ II cyclam were studied within the host molecule to calculate the interaction energy and free energy of association for each complex. The relative free energies of the five free cyclams confirm that trans -I and trans -II are the most energetically accessible diastereoisomers from the initial trans -III starting point. Energy decomposition analysis was used to identify the attractive and repulsive interactions between cyclam and cucurbit[8]uril and showed that trans -II encounters repulsive forces almost three times greater than trans -I, which may explain the 7:3 ratio of trans -I to trans -II within cucurbit[8]uril that occurs experimentally. Optimized complex geometries with trans -III, IV, and V show that the cyclams protrude out of cucurbit[8]uril, whereas trans -I and trans -II become more encapsulated and elongate the host, suggesting that the position of the cyclam is extremely important when forming non-covalent interactions. Our results agree with the experimental findings and provide greater insight into why the most stable isolated cyclam diastereoisomer, trans -III, does not form a complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ultrafast X-ray Spectroscopy of Intersystem Crossing in Hexafluoroacetylacetone: Chromophore Photophysics and Spectral Changes in the Face of Electron-Withdrawing Groups

Intersystem crossings between singlet and triplet states represent a crucial relaxation pathway in photochemical processes. Herein, we probe the intersystem crossing in hexafluoro-acetylacetone with ultrafast X-ray transient absorption spectroscopy at the carbon K-edge. In this study, we observe the excited state dynamics following excitation with 266 nm UV light to the 1 ππ* (S 2 ) state with element and site-specificity using a broadband soft X-ray pulse produced by high harmonic generation. These results are compared to X-ray spectra computed from orbital optimized density functional theory methods. It is found that the electron-withdrawing fluorine atoms decongest the X-ray absorption spectrum by enhancing separation between features originating from different carbon atoms. This facilitates the elucidation of structural and electronic dynamics at the chromophore. The evolution of the core-to-valence resonances at the carbon K-edge reveals an ultrafast population transfer between the 1 nπ* (S 1 ) and 3 ππ* (T 1 ) states on a 1.6 ± 0.4 ps time scale, which is similar to the 1.5 ps time scale earlier observed for acetylacetone [ J. Am. Chem. Soc. 2017, 139, 16576—16583, DOI: 10.1021/jacs.7b07532]. It therefore appears that terminal fluorination has little influence on the intersystem crossing rate of the acetylacetone chromophore. In addition, the significant role of hydrogen-bond opened and twisted rotational isomers is elucidated in the excited state dynamics by comparison of the experimental transient X-ray spectra with theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Experimental Verification of An Electro-Hydraulic Actuation System Driven by An Integrated Electro-Hydraulic Unit

This paper proposes an electro-hydraulic actuator (EHA) system, and a novel-designed electro-hydraulic unit (EHU) consisting of a fixed-displacement hydraulic gear machine and a variable-speed electric machine. The novel EHU design integrates an electric machine and a hydraulic machine in a single housing, targeting optimal compactness, power density, and component reduction. The EHA system features an open circuit design, where hydraulic hoses connect the EHU with a tank, a valve manifold, and the hydraulic cylinder. In this way, the proposed EHA technology can be used to implement distributed hydraulic actuation in a vehicle without requiring changes to the hydraulic actuators or at the overall layout of the hydraulic components with respect to the original vehicle design. A dedicated test rig is developed to verify the performance of the proposed EHA system. Here, the efficiency of the EHA is measured in a steady state and under a realistic duty cycle of a commercial compact loader. The efficiency of the EHA system based on the measurements on the test rig can reach 54% with up to 20 kN load and 6 kW power level. Furthermore, the EHU is implemented on the reference machine to drive the boom function. Preliminary results on the performance of the EHU show an efficiency of up to 68% under different loading conditions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2014

Poster — Thur Eve — 18: Cherenkov Emission By High-Energy Radiation Therapy Beams: A Characterization Study

We investigate Cherenkov emission (CE) by radiotherapy beams via radiation dose-versus-CE correlation analyses, CE detection optimization by means of a spectral shift towards the near-infrared (NIR) window of biological tissue, and comparison of CE to on-board MV imaging. Dose-CE correlation was investigated via simulation and experiment. A Monte Carlo (MC) CE simulator was designed using Geant4. Experimental phantoms include: water; tissue-simulating phantom composed of water, Intralipid®, and beef blood; plastic phantom with solid water insert. The detector system comprises an optical fiber and diffraction-grating spectrometer incorporating a front/back-illuminated CCD. The NIR shift was carried out with CdSe/ZnS quantum dots (QDs), emitting at (650±10) nm. CE and MV images were acquired with a CMOS camera and electronic portal imaging device. MC and experimental studies indicate a strong linear dose-CE correlation (Pearson coefficient > 0.99). CE by an 18-MeV beam was effectively NIR-shifted in water and a tissue-simulating phantom, exhibiting a significant increase at 650 nm for QD depths up to 10 mm. CE images exhibited relative contrast superior to MV images by a factor of 30. Our work supports the potential for application of CE in radiotherapy online imaging for patient setup and treatment verification, since CE is intrinsic to the beam and non-ionizing and QDs can be used to improve CE detectability, potentially yielding image quality superior to MV imaging for the case of low-density-variability, low-optical-attenuation materials (ex: breast/oropharynx). Ongoing work involves microenvironment functionalization of QDs and application of multi-channel spectrometry for simultaneous acquisition of dosimetric and tumor oxygenation signals.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2018

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

Recently, a series of double-perovskite halide compounds such as Cs 2 AgBiCl 6 and Cs 2 AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3 NH 3 PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Cs 2 AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2 AgBr 3 , Cs 3 Bi 2 Br 9 , etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Density functional study of atomic arrangements in CrMnFeCoNi high-entropy alloy and their impact on vacancy formation energy and segregation

Here, using the density functional theory-coupled Monte Carlo approach, we explored the chemical short-range order (SRO) and element segregation in equimolar CrMnFeCoNi alloy. We found that state-of-the-art approximation of random element distribution is only applicable at > 1100 K close to the melting temperature, while the Cr-Cr repulsion driving the system stabilization and accompanying the formation of cubic Cr sublattice, and mild Ni-Ni attraction are the most prominent pair interactions at lower temperatures. Chemical potential and vacancy formation energy calculations indicate that Cr is most sensitive to the local chemical environment, making Cr atoms most stabilized when the preferred SRO is introduced. While the vacancy formation is predicted equally probable among five constituting elements in the random solid solution, Cr and Ni atoms show the lowest vacancy formation energies in the structure with SRO. Furthermore, distinct element segregation was predicted in the vicinity of planar defects, including symmetric tilt grain boundary and stacking fault, which we correlated to the site- and chemistry-dependent atomic volume and bond lengths. It suggests that the local mechanical strain and bond energy induce the SRO development and element segregation: Namely, the system takes advantage of segregation of Ni atoms having large atomic volume or Cr-Cr pairs having elongated bond lengths to fill in the excess volume at defects that relaxes the mechanical strain field and optimizes bond energy distribution. The correlation between the SRO and properties of CrMnFeCoNi alloy needs further investigations, which is expected to greatly help understand and control the properties of high-entropy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Downward quantum learning from element 118: Automated generation of Fermi–Löwdin orbitals for all atoms

A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi–Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew–Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N – 1 and a maximum of 2 N – 2 initial starting points for systems composed of a smaller number of electrons. As a result, applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effects of support and promoter on Ru catalyst activity in microwave-assisted ammonia synthesis

Microwave-assisted ammonia synthesis is a promising alternative to the energy-intensive Haber-Bosch process, specially at small- and medium-scale with renewable H 2 as resource. Here, we report that Cs promoted Ru/CeO 2 catalyst exhibits considerable activity at 533 K and ambient pressure. In this work, the combined theoretical and experimental approaches are adopted to optimize the electronic and geometric structures of Ru on the catalysts. Both DFT modeling work and structural characterization show that the strong interaction between Ru and CeO 2 results in the formation of highly dispersed Ru particles favoring ammonia synthesis. The higher electron donating ability of CeO 2 and lower electronegativity of Cs promoter result in higher electron density on Ru reducing the N≡N dissociation barrier. Finally, the work demonstrates the potential of microwave-assisted catalytic process in activating stable molecules for ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

An In Situ Surface-Enhanced Infrared Absorption Spectroscopy Study of Electrochemical CO 2 Reduction: Selectivity Dependence on Surface C-Bound and O-Bound Reaction Intermediates

The CO2 electroreduction reaction (CO2RR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long been known to be unique in their capabilities of catalyzing the conversion of CO2 to higher-order C1 and C2 fuels, such as hydrocarbons (CH4, C2H4, etc.) and alcohols (CH3OH, C2H5OH), product selectivity remains a challenge. Rational design of more selective catalysts would greatly benefit from a mechanistic understanding of the complex, multiproton, and multielectron conversion of CO2. In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced infrared absorption spectroscopy (SEIRAS) and ambient-pressure X-ray photoelectron spectroscopy (APXPS), coupled to density-functional theory (DFT) calculations, to get insight into the reaction pathway for the CO2RR. We present a comprehensive reaction mechanism for the CO2RR and show that the preferential reaction pathway can be rationalized in terms of metal–carbon (M–C) and metal–oxygen (M–O) affinity. We show that the final products are determined by the configuration of the initial intermediates, C-bound and O-bound, which can be obtained from CO2 and (H)CO3, respectively. C1 hydrocarbons are produced via OCH3,ad intermediates obtained from O-bound CO3,ad and require a catalyst with relatively high affinity for O-bound intermediates. Additionally, C2 hydrocarbon formation is suggested to result from the C–C coupling between C-bound COad and (H)COad, which requires an optimal affinity for the C-bound species, so that (H)COad can be further reduced without poisoning the catalyst surface. It is suggested that the formation of C1 alcohols (CH3OH) is the most challenging process to optimize, as stabilization of the O-bound species would both accelerate the formation of key intermediates (OCH3,ad) but also simultaneously inhibit their desorption from the catalyst surface. Our findings pave the way toward a design strategy for CO2RR catalysts with improved selectivity, based on the experimental/theoretical reaction mechanisms that have been identified. These results also suggest that designing the electronic structure of the catalyst is not the sole determining factor to achieve highly selective CO2RR catalysis; rather, tuning additional experimental reaction conditions such as electrolyte–intermediate interactions also become critical.

Katayama, Yu↗
DOE OSTI2022

Three-dimensional Skyrme Hartree-Fock-Bogoliubov solver in coordinate-space representation

The coordinate-space representation of the Hartree-Fock-Bogoliubov theory is the method of choice to study weakly bound nuclei whose properties are affected by the quasiparticle continuum space. To describe such systems, we developed a three-dimensional Skyrme-Hartree-Fock-Bogoliubov solver HFBFFT based on the existing, highly optimized and parallelized Skyrme-Hartree-Fock code Sky3D. The code does not impose any self-consistent spatial symmetries such as mirror inversions or parity. The underlying equations are solved in HFBFFT directly in the canonical basis using the fast Fourier transform. To remedy the problems with pairing collapse, we implemented the soft energy cutoff and pairing annealing. The convergence of HFB solutions was improved by a sub-iteration method. The Hermiticity violation of differential operators brought by Fourier-transform-based differentiation has also been solved. Furthermore, the accuracy and performance of HFBFFT were tested by benchmarking it against other HFB codes, both spherical and deformed, for a set of nuclei, both well-bound and weakly-bound.

3D coordinate-space representation↗
DOE OSTI2019

Fundamental Insights into the Reactivity and Utilization of Open Metal Sites in Cu(I)-MFU-4 l

Metal organic frameworks (MOFs) having open metal sites have the potential to approach the activity of homogeneous organometallic complexes, thus combining the advantages of homogeneous and heterogeneous catalysis. We pre-sent a fundamental study of the effectiveness of incorporating open metal sites into MOFs. We have modeled the binding of a series of adsorbates in a Cu(I) substituted MOF, Cu(I)-MFU-4l using density functional theory, and compared the activity of the Cu(I) sites in Cu(I)-MFU-4l with two different Cu(I) scorpionate complexes. The computational results confirm the single-site nature of the Cu(I) active site. This is further supported by complementary experiments to measure the chemisorption uptake inside our synthesized samples in order to estimate the amount of active Cu sites present. We observed a level of chemisorption that is roughly half the theoretical maximum, which implies that only half of the Cu atoms incorporated into MFU-4l via metal-ion exchange are able to act as binding sites. We speculate that the inactive Cu atoms are coordinately saturated Cu(II) sites. Furthermore, our work suggests that the performance of Cu(I)-MFU-4l could be significantly increased by optimizing the metal exchange and activation processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Excited State Dynamics of a Conformationally Fluxional Copper Coordination Complex

The conversion of solar energy into chemical fuel represents a capstone goal of the 21st century and has the potential to supply terawatts of power in a globally distributed manner. However, the disparate time scales of photodriven charge separation (~fs) and steps in chemical reactions (~μs) represent an inherent bottleneck in solar-to-fuels technology. Here to address this discrepancy, we are developing earth-abundant coordination complexes that undergo light-induced conformational rearrangements such that charge separation (CS) is hastened, while charge recombination (CR) is slowed. To these ends, we report the preparation and characterization of a new series of conformationally fluxional copper coordination complexes that contain a twisted intramolecular charge transfer (TICT) fluorophore as part of their ligand scaffold. Structural and spectroscopic characterization of the Cu(I) and Cu(II) complexes formed with these ligands in their ground states establish oxidation state-dependent conformational dynamicity, while time-resolved emission and transient absorption spectroscopies define the photopysical parameters of photo-induced excited states. Building on initial reports with a related set of molecules, the improved ligand design presented here greatly simplifies the observed photophysics, effectively shutting down unwanted ligand-centered excited states previously observed. Finally, time-dependent density functional theory (TDDFT) analyses reveal an unusual metal-to-TICT electronic transition only reported once before, and though the formation of a CS state is not observed directly through experiments, TDDFT geometry optimizations in the excited states support the formation of transient Cu(II) CS species, lending credence to the potential success of our approach. These studies establish a clear model for the excited state dynamics at play in proof-of-concept systems and clarify key design parameters for future optimizations toward achieving long-lived CS via photoinduced conformational gating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Precision Agriculture using Networks of Degradable Analytical Sensors (PANDAS) (Final Technical Report)

Precision agriculture, where sensing of soil, environment and crop conditions are used to precisely synchronize inputs (such as water and fertilizer) to crop needs enhances input use efficiency. This can improve yields and farm profitability while mitigating environmental losses, improving soil carbon content and substantially decreasing energy use for food, feed and fuel crops. Unfortunately, farmers are not yet able to harness the full potential of these management technologies as there is a lack of available management information, and there is therefore a need for sensors that are able to economically measure spatio-temporal variability in soil and crop properties of extremely heterogeneous farm fields precisely at high resolution and at low cost. Real-time, in-situ monitoring of agricultural soil conditions is today carried out using devices that limit the total number of nodes that can be used economically to typically one per acre or less. Higher spatio-temporal resolution sensing would enable more precise agricultural input optimization, with significant benefits to the farmer and the environment. In order to address this issue, this project focused on developing additively manufactured, biodegradable, soil sensors with predicted costs of < $\$$1 per unit to monitor crop inputs (such as water and fertilizer) that predictably, harmlessly degrade away into the soil when no longer needed. These sensor nodes should be easy to place, accurately and continuously monitor soil and crop conditions for an entire season, be read remotely using existing farm equipment, require no ongoing maintenance, not impede farm operations and produce no persistent waste. This approach could enable a >100× increase in information density over current solutions for precision farming of row and other crops, and lead to significant reductions in input energy use and provide increased yield for biofuel crops. Over the course of this project the team at the University of Colorado Boulder, University of California Berkeley, and Colorado State University/Kansas State University investigated a wide range of printable biodegradable electronic materials and sensor designs for determining soil moisture and soil nitrate concentration. These efforts expanded the available materials set for printed soil degradable electronic materials, particularly for conductors, enabling high conductivity and stability. Printed soil moisture and nitrate sensors with suitable sensitivity and selectivity were developed and characterized. Low power and passive wireless electronic systems were integrated with the soil sensors, and testing was carried out with completed sensors to understand their functionality under agricultural conditions. Additionally, other sensor types enabled by the biodegradable materials set created during this project, such as soil microbial activity sensors, were also developed and demonstrated. Project outputs include 10 peer reviewed publications, 4 patent applications, 21 technical presentations, 3 PhD thesis, 10 media reports, 8 additional grants worth over $\$$6M, and the formation of 3 start-up companies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Artificial intelligence inferred microstructural properties from voltage–capacity curves

Abstract The quantification of microstructural properties to optimize battery design and performance, to maintain product quality, or to track the degradation of LIBs remains expensive and slow when performed through currently used characterization approaches. In this paper, a convolution neural network-based deep learning approach (CNN) is reported to infer electrode microstructural properties from the inexpensive, easy to measure cell voltage versus capacity data. The developed framework combines two CNN models to balance the bias and variance of the overall predictions. As an example application, the method was demonstrated against porous electrode theory-generated voltage versus capacity plots. For the graphite|LiMn $$_2$$ 2 O $$_4$$ 4 chemistry, each voltage curve was parameterized as a function of the cathode microstructure tortuosity and area density, delivering CNN predictions of Bruggeman’s exponent and shape factor with 0.97 $$R^2$$ R 2 score within 2 s each, enabling to distinguish between different types of particle morphologies, anisotropies, and particle alignments. The developed neural network model can readily accelerate the processing-properties-performance and degradation characteristics of the existing and emerging LIB chemistries.

25 ENERGY STORAGE↗